Fluorovinyl ethers and polymers obtainable therefrom

ABSTRACT

Fluorovinyl ethers having the formula CFX═CXOCF 2 OR, wherein R is a C 2 -C 6  linear, branched or C 5 -C 6  cyclic (per)fluoroalkyl group, or a C 2 -C 6 , linear, branched (per)fluoro oxyalkyl group containing from one to three oxygen atoms; when R is fluoroalkyl or fluorooxyalkyl group as above defined, it can contain from 1 to 2 atoms, equal or different, selected from the following: H, Cl, Br, I; X═F, H; and homopolymers or polymers obtainable polymerizing said Fluorovinyl ethers with at least another polymerizable monomer.

[0001] The present invention relates to Fluorovinyl ethers, the process for preparing them and the polymers obtainable therefrom.

[0002] It is well known that perfluoroalkyl vinyl ethers are generally used as monomers for the olefin copolymerization, specifically copolymerization with tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene (CTFE), and/or hexafluoropropene. The introduction of small amounts of perfluoroalkyl vinyl ethers in plastomeric polymers implies a higher polymer processability and better hot mechanical properties. The introduction of high amounts of perfluorovinyl ethers in crosslinkable fluoropolymers implies elastomeric oroperties at low temperature of fluorinated rubbers.

[0003] The need was felt, in the fluorinated polymeric material field, to produce both plastomers having good properties at high temperatures, and elastomers having improved properties at low temperatures by using only one fluorovinyl ether.

[0004] Such properties at low temperatures can generally be expressed by the glass transition temperature Tg.

[0005] Furthermore the need was felt to have available amorphous or crystalline copolymers having a low content of C(O)F end groups. A lower content of C(O)F end groups leads to obtain polymers having a higher thermal stability. A lower Tg allows to have elastomeric polymers which can be used at lower temperatures and therefore to have available elastomers with a wider use range. To obtain the combination of the above mentioned properties, fluorovinyl ethers must have a high unitary capability to modify the base backbone properties, as well as high reactivity to be used as comonomers both in plastomeric and in elastomeric fluoropolymers. It was desirable to have available vinyl ethers obtainable by simple processes having a limited number of steps. Preferably it would be desirable to have available a continuous process for preparing said vinyl ethers.

[0006] To solve the above identicated technical problem, fluorovinyl ethers having different structural properties, have been proposed in the prior art. However from the prior art, hereinafter described, various unsolved problems result evident in the perfluorovinyl ether synthesis and in the preparation of the correspondig polymers having the combination of the above mentioned properties.

[0007] U.S. Pat. No. 3,132,123 describes the preparation of perfluoroalkyl vinyl ethers, of the corresponding homopolymers and copolymers with TFE. Homopolymers are obtained under extreme experimental conditions, by using polymerization pressures from 4,000 to 18,000 atm. The perfluoromethylvinylether (PMVE) homopolymer is an elastomer: the Tg is not reported.

[0008] The general formula of the described vinyl ethers is the following:

CF₂═CFOR^(O) _(F)

[0009] wherein R^(O) _(F) is a perfluoroalkyl radical preferably from 1 to 5 carbon atoms. A process for preparing these vinyl ethers is described in U.S. Pat. No. 3,291,843 wherein the starting acylfluoride is salified and pyrolized with carbonates also in the presence of solvents. By this process undesired hydrogenated by products are obtained.

[0010] U.S. Pat. No. 3,450,684 relates to vinyl ethers having the formula:

CF₂═CFO(CF₂CFX⁰O)_(n), CF₂CF₂X⁰

[0011] wherein X⁰=F, Cl, CF₃, H and n′ can range from 1 to 20. Also homopolymers obtained by UV polymerization are reported. The exemplified copolymers are not characterized by their properties at low temperatures.

[0012] U.S. Pat. No. 3,635,926 relates to the emulsion copolymerization of perfluorovinyl ethers with TFE, showing that the presence of —C(O)F acylfluoride end groups makes the polymers unstable. The same phenomenon was already reported in U.S. Pat. No. 3,085,083 in the perfluorovinyl ether polymerization systems in solvent.

[0013] U.S. Pat. No. 3,817,960 relates to the preparation and polymerization of perfluorovinyl ethers having the formula

CF₃O(CF₂O)_(n″)CF₂CF₂OCF═CF₂

[0014] wherein n″ can range from 1 to 5. The compound synthesis is complex, it requires three steps. The preparation of the starting compound CF₃O(CF₂O)_(n″)CF₂C(O)F is carried out by oxidation at low temperature in the presence of U.V. radiations; besides the condensation with HFPO (hexafluoropropenoxide) and the subsequent alkaline pyrolisis is necessary. No data on the above indicated properties are reported. With regard to this see patent application U.S. Pat. No. 5,910,552.

[0015] U.S. Pat. No. 3,896,179 relates to the separation of “primary” isomers of perfluorovinyl ethers, for example of CF₃CF₂CF₂OCF═CF₂ from the corresponding less stable “secondary” isomers CF₃ (CF₃) CFOCF═CF₂. The latter are undesired products as regards both the polymer preparation and the poor properties of the obtained polymers.

[0016] U.S. Pat. No. 4,340,750 relates to the preparation of perfluorovinyl ethers having the formula

CF₂═CFOCF₂R^(o) _(f)X¹

[0017] wherein R^(o) _(f) is a C₁-C₂₀ perfluoroalkyl optionally containing oxygen, X¹=H, Cl, Br, F, COOR^(o), CONR^(o)R′ wherein R^(o) is a C₁-C₁₀ alkyl group and R′ represents H or a C₁-C₁₀ alkyl group. In the preparation of these compounds an acylfluoride together with iodine and tetrafluoroethylene is used, avoiding the final step of the acylfluoride pyrolisis which comes from the perfluoro-propene epoxide, by a deiodofluorination reaction, which takes place with low yields.

[0018] U.S. Pat. No. 4,487,903 relates to the preparation of fluoroelastomeric copolymers (i.e., elastomeric fluoropolymers) using perfluorovinyl ethers having the formula:

CF₂═CF(OCF₂CFY^(O))_(n) ^(o)OX²

[0019] wherein n⁰ ranges from 1 to 4; Y^(o)=F, Cl, CF₃, H; X² can be C₁-C₃ perfluoroalkyl group, C₁-C₃ ω-hydroperfluoroalkyl group, C₁-C₃ ω-chloroperfluoroalkyl group. The polymer has a content of fluorovinyl ether units ranging from 15 to 50% by moles. These vinyl ethers give copolymers which at low temperatures have better properties than those of the above mentioned perfluorovinyl ethers PVE (perfluoropropyl vinyl ether) and MVE type. In the patent it is disclosed that in order to have good properties at low temperature, the presence of at least two ether bonds in the side chain adjacent to the double bond is required. Furthermore from the patent it results that for values higher than 4 it is difficult to purify the monomers and the effect on the decrease of the polymer T_(g) is lower. Besides the reactivity of the described vinyl ethers is very low and it is difficult to obtain polymers having a high molecular weight able to give good elastomeric properties. A TFE/perfluorovinyl ether copolymer (n^(o)=2) 73/27% by moles with Tg of −32° C. is exemplified. However the polymer is obtained with very long reaction times (96 hours of polymerization).

[0020] Patent EP 130,052 describes the perfluoro(vinyl polyether) (PVPE) polymerization which leads to amorphous perfluoropolymers with a T_(g) ranging from −15 to −100° C. The described polymers have T_(g) values reaching up to −76° C.; the further T_(g) decrease is obtained by using perfluoropolyethers as plasticizers. In the patent copolymers and terpolymers of TFE and MVE with vinylethers (PVPE) having the formula

CF₂═CFO(CF₂CF(CF₃)0)_(n′″)R^(o) _(f),

[0021] are described, wherein n′″ ranges from 3 to 30 and R^(o) _(f), is a perfluoroalkyl group. Due to purification difficulties, the used vinyl ethers are vinylether mixtures with different n′″ values. According to said patent the most evident effect on the T_(g) decrease is shown when n′ is equal to or higher than 3, preferably higher than 4. According to the polymerization examples described in said patent the final mass of the polymer, besides the hot and under vacuum treatment, must then be washed with freon® TF in order to remove all the unreacted monomer (PVPE). From the Examples it results that the reactivity of all the described monomers (PVPE) is poor.

[0022] U.S. Pat. No. 4,515,989 relates to the preparation of new intermediates for the fluorovinyl ether synthesis. According to the patent the vinylether synthesis is improved by using an intermediate able to more easily decarboxylate. For its preparation fluoroepoxides of formula:

[0023] wherein X³=Cl, Br are used.

[0024] U.S. Pat. No. 4,619,983 describes the copolymerization of VDF with vinyl ethers having the formula:

CF₂═CFOX⁴

[0025] wherein X⁴ is a C₃-C₉ oxyperfluoroalkyl radical containing from 1 to 3 oxygen atoms. The obtained polymers are not perfluorinated polymers and show a poor stability to alcohols.

[0026] U.S. Pat. No. 4,766,190 relates to the polymerization of perfluorovinylpolyethers (PVPE) similar to those of U.S. Pat. No. 4,487,903 with TFE and low perfluoropropene percentages, in order to increase the mechanical properties of the obtained polymers.

[0027] Patent EP 338,755 relates to the preparation of perfluorinated copolymers by using direct fluorination of partially fluorinated copolymers. More reactive partially fluorinated monomers are used, subjecting the obtained polymers are fluorinated with elemental fluorine. The fluorination step requires a supplementary process unit, besides in this step elemental fluorine is used, which is a highly oxidizing gas, with the consequent precautions connected to its use. Besides in the patent it is stated that in order not to compromise the fluorination reaction and the properties of the obtained polymer, using the invention process the percentage of the comonomer in the polymer cannot exceed 50% by moles.

[0028] U.S. Pat. No. 5,268,405 reports the preparation of perfluorinated rubbers having a low Tg, by the use of high viscosity perfluoropolyethers as plasticizers of perfluorinated rubbers (TFE/MVE copolymers). However during the use perfluoropolyether bleeds take place. This is true especially for the PFPE having a low molecular weight (low viscosity): in said patent, therefore, the high viscosity PFPE use is suggested, and therefore the low viscosity PFPEs must previously be removed from these last.

[0029] U.S. Pat. No. 5,350,497 relates to the preparation of perfluoroalkyl vinyl ethers by fluorination with elemental fluorine of hydrofluorochloroethers and subsequent dechlorination.

[0030] U.S. Pat. No. 5,401,818 relates to the prepartion of perfluorovinyl ethers of formula:

R¹ _(f)(OCF₂CF₂CF₂)_(m), —OCF═CF₂

[0031] (wherein R¹ _(f) is a C₁-C₃ perfluoroalkyl radical and m, is an integer ranging from 1 to 4) and of the corresponding copolymers having improved properties at low temperature. The preparation of said perfluorovinyl ethers is carried out by 7 steps, some of them have very low yields, and comprise also a fluorination with elemental F₂. The reactivity of said perfluorovinyl ethers is anyhow low.

[0032] As it is shown from the above prior art, the perfluorovinyl ether synthesis generally involves a multistep process with low yields (U.S. Pat. No. 3,132,123, U.S. Pat. No. 3,450,684), with additional purifications to remove undesired isomers (U.S. Pat. No. 3,896,179) and the need to control the undesired hydrogenated by-products (U.S. Pat. No. 3,291,843). Alternatively, in the synthesis substances acting as intermediates, which are suitably prepared, and which allow to eliminate said drawbacks (U.S. Pat. No. 4,340,750, U.S. Pat. No. 4,515,989), are used.

[0033] Furthermore in some cases the vinylether preparation requires the fluorination with elemental fluorine of partially fluorinated intermediates (U.S. Pat. No. 5,350,497); or, to avoid synthesis and low reactivity problems of the perfluorovinyl ethers, fluorination of partially fluorinated polymers (EP 338,755) is suggested.

[0034] Other problems shown in the prior art relate to the low reactivity of the perfluorovinyl ethers, which makes it necessary the recovery of the unreacted monomers from the reaction raw products (English Patent UK 1,514,700), and the stability problems for the polymers having —C(O)F end groups (U.S. Pat. No. 3,635,926). These last can be furtherly transformed by suitable reactants in order to increase the stability of the fluorinated polymer (EP 178,935).

[0035] Perfluoro(oxyalkyl vinyl ethers) are used to confer to the fluorinated rubbers good properties at low temperatures, and specifically to lower the copolymer glass transition temperature.

[0036] By increasing the perfluorooxyalkyl units forming the side perfluorooxyalkyl substituent, the T_(g) of the corresponding obtainable amorphous copolymers decreases, but at the same time the vinylether reactivity drastically decreases, making more evident the problems previously shown for the recovery of the unreacted monomer from the raw polymerization products or from the polymer itself (U.S. Pat. No. 4,487,903-EP 130,052). In some cases, where the monomer cannot be completely removed by simple stripping under vacuum, more washings must then be carried out with fluorinated solvents for completely eliminating the unreacted vinyl ethers from the polymeric mass.

[0037] The perfluoromethylvinylether (MVE) is used as comonomer in plastomeric fluoropolymers and, at higher concentrations, also in elastomeric fluoropolymers. In particular in, EP 633,257 and EP 633,274 MVE is polymerized with TFE in the presence of small amounts of PVE or dioxoles to obtain polymers with improved flex life.

[0038] The amorphous copolymers of TFE with perfluoromethyl-vinylether have a T_(g) around 0° C. or slightly lower (Maskornik, M. et al. “ECD-006 Fluoroelastomer—A high performance engineering material”. Soc. Plast Eng. Tech. Pao. (1974), 20, 675-7).

[0039] The T_(g) extrapolated value of the MVE homopolymer is of about −5° C. (J. Macromol. Sci.-Phys., B1(4), 815-830, December 1967).

[0040] In U.S. Pat. Nos. 5,296,617 and 5,235,074 there is described the hypofluorite CF₂(OF)₂ reactivity towards unsaturated products, which contemporaneously leads to the formation of the dioxolane derivative and to the fluorination compound of the olefin itself. In Patent EP 683,181 there is described the CF₂(OF)₂ reactivity towards olefins which leads to the formation of linear reaction compounds between one hypofluorite molecule and two molecules of the same olefin, for the preparation of symmetric dienes.

[0041] The Applicant has surprisingly and unexpectedly found that it is possible to solve the above mentioned technical problems, by using special fluoro vinyl ethers that are furthermore easily synthesizable and obtainable by a continuous process.

[0042] An object of the present invention are fluorovinyl ethers of general formula:

CFX═CXOCF₂OR  (I)

[0043] wherein R is a C₂-C₆ linear, branched or C₅-C₆ cyclic (per)fluoroalkyl group, or a C₂-C₆ linear, branched (per)fluoro oxyalkyl group containing from one to three oxygen atoms; when R is a fluoroalkyl or fluorooxyalkyl group as above defined it can contain from 1 to 2 atoms, equal to or different from each other, selected from the following: H, Cl, Br, I; X═F, H. The term (per)fluoro refers to a molecule in which from one up to all of the hydrogens capable of beign replaced with fluorine are replaced with fluorine.

[0044] The fluorovinyl ethers of general formula:

CFX═CXOCF₂OCF₂CF₂Y  (II)

[0045] wherein Y═F, OCF₃; X as above defined, are preferred among the compounds of formula (I).

[0046] The perfluorovinyl ethers of formula:

CF₂═CFOCF₂OCF₂CF₂Y  (III)

[0047] wherein Y is as above defined, are furtherly preferred. For example the perfluorovinyl ether having the formula:

CF₂═CFOCF₂OCF₂CF₃  (IV)

[0048] can be mentioned.

[0049] Surprisingly, the vinyl ethers according to the invention show the advantages reported hereinafter with respect to the known vinyl ethers.

[0050] The obtainable advantages can be attributed to the —OCF₂O— unit directly bound to the ethylene unsaturation.

[0051] The Tg lowering obtained with the vinyl ethers of the invention is connected to the presence of the (—OCF₂O—) unit directly bound to the unsaturation. The Tg lowering is surprisingly so evident to be defined a primary effect.

[0052] In fact if the vinylether of the invention with two oxygen atoms is used:

CF₂═CF—O—CF₂—O—CF₂CF₃  (MOVE 1)

[0053] the Tg lowering is clearly higher with respect to the Tg of the polymer from PVE

CF₂═CF—O—CF₂CF₂CF₃  (PVE)

[0054] and to the vinyl ether having the same formula, but with the second oxygen atom in a different position and without showing the characteristic unit (—OCF₂O—)

CF₂═CF—O—CF₂CF₂—O—CF₃  (β-PDE)

[0055] It is surprising to notice that with respect to MVE

CF₂═CF—O—CF₃

[0056] the β-PDE vinyl ether does not give any advantage as regards Tg.

[0057] On the contrary the primary effect of the (—OCF₂O—) unit results very clear with the vinyl ethers of the invention (MOVE).

[0058] Besides it has surprisingly been found that the (—OCF₂O—) unit bound to the ethylene unsaturation of the vinyl ethers of the invention increases the vinylether reactivity drastically reducing the rearrangements to C(O)F which cause instability.

[0059] The advantages of the polymers of the invention can be summarized as follows:

[0060] The reactivity of the new monomers allows to prepare copolymers having a high MW (molecular weight) with a very low content of carboxylic groups or derivatives thereof such as —C(O)F, —COO—. The carboxylic group content in the copolymer of a monomer of the present invention with TFE has resulted of about 10 times lower than that of a copolymer prepared under the same conditions but using perfluoropropyl vinyl ether (PVE) instead of fluorovinyl ethers (see the Examples). As said, the presence of a lower content of carboxylic groups, or of the corresponding derivatives (amides, esters, etc.) results in more stable polymers.

[0061] The reactivity of the monomers of the invention is surprisingly high (see the homopolymerization Examples). The fluorovinyl ethers of the invention can be used as comonomers both in plastomeric (per)fluoropolymers (containing crystalline domains) and in elastomeric (per)fluoropolymers. To obtain plastomeric polymers the amount of the vinylether of the invention must be such to allow and lead to the formation of crystalline domains, generally <10% by moles. The presence of crystalline domains can be determined by DSC. To obtain amorphous polymers the amount of the vinylether of the invention must be such to lead to the disappearance of the crystalline domains. The skilled man in the art can easily find the amount of the vinylether of the invention which is required for obtaining said results. The novel fluorovinyl ethers of the present invention can be used in amounts as low as about 0.1% on a mole basis. Generally the amount of the vinyl ether for obtaining amorphous polymers is higher than 10% by moles (i.e. 10 mole %), preferably in the range from about 15 to 20% by moles, or higher. In the case of copolymers having a high content of vinyl ether monomer, the properties at low temperature (T_(g)) of the polymers of the invention result clearly better with respect both to copolymers having the same MVE content (see the Examples) and also, surprisingly, with respect to copolymers where the perfluorovinyl ether, the oxygen atoms being equal, does not show the —OCF₂Ogroup directly bound to the unsaturation, as in the case of the CF₂═CFOCF₂CF₂OCF₃ (β-PDE) (see the Examples).

[0062] Their use in the polymerization reactions with fluoroolefins allows to substantially and contemporaneously reduce two important disadvantages of the prior art: the recovery of the unreacted vinylether and the polymer instability due to the presence of carboxylic end groups. A further advantage of the fluorovinyl ethers of the invention, as hereinafter illustrated, consists in that their preparation is carried out in a continuous plant by a limited number of steps. Furthermore the used raw materials are inexpensive. The following raw materials can for example be mentioned: CF₂(OF)₂, CF₂═CF₂CF₂═CFOCF₃, CHCl═CFCl, CFCl═CFCl, CF₂═CFCl, CF₂═CFH, CF₂═CH₂, CHCl═CHCl and other olefins. The use of these reactants is specified in the synthesis process of the vinyl ethers of the invention.

[0063] When used in connection with a quantity the term about refers to such normal variation in that quantity as would be expected by the skilled artisan.

[0064] As used herein, essentially free of crystalline zones or regions means that crystallinity is not detected by, for example, DSC, under typical ordinary conditions as would be used by the skilled artisan in routine experiments.

[0065] Polymers, homopolymers and copolymers are obtainable by polymerizing the fluorovinyl ethers of general formula (I)-(IV) alone or with at least another monomer.

[0066] With copolymer, a polymer containing the vinyl ether of the invention and one or more comonomers, is meant.

[0067] Preferred comonomers are fluorinated compounds having at least one polymerizable double bond C═C, optionally containing hydrogen and/or chlorine and/or bromine and/or iodine and/or oxygen.

[0068] Other comonomers that can be copolymerized within the fluorovinyl ethers of the present invention are non fluorinated C₂-C₈ olefins, i.e. olefinically unsulated hydrocarbons such as ethylene, propylene, isobutylene.

[0069] Among the usable comonomers the following can be mentioned:

[0070] C₂-C₈ perfluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropene (HFP), hexafluoroisobutene;

[0071] C₂-C₈ hydrogenated fluoroolefins, such as vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene, CH₂═CH—R² _(f) perfluoroalkylethylenes, wherein R² _(f) is a C₁C₆ perfluoroalkyl group;

[0072] C₂-C₈ chloro- and/or bromo- and/or iodo-fluoroolefins, such as chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene;

[0073] CF₂═CFOR² _(f) (per)fluoroalkyl vinyl ethers (PAVE), wherin R² _(f) is a C₁-C₆ (per)fluoroalkyl group, for example a trifluoromethyl, bromodifluoromethyl or a heptafluoropropyl group;

[0074] CF₂═CFOX^(a) (per)fluoro-oxyalkylvinyl ethers, wherein X^(a) is: a C₁-C₁₂ alkyl, or a C₁-C₁₂ oxyalkyl group, or a C₁-C₁₂ (per)fluorooxyalkyl group having one or more ether groups, for example perfluoro-2-propoxypropyl.

[0075] sulphonic monomers having the structure CF₂═CFOX^(b)SO₂F, wherein X^(b)=CF₂CF₂, CF₂CF₂CF₂, CF₂CF(CF₂X^(c)) wherein X^(c)=F, Cl, Br.

[0076] The process for preparing fluorinated polymers according to the present invention can be carried out by polymerization in organic solvent as described in U.S. Pat. Nos. 4,864,006 and 5,182,342, herein incorporated by reference. The organic solvent is selected from the group including chlorofluorocarbons, perfluoropolyethers, hydrofluorocarbons and hydrofluoroethers.

[0077] The process for preparing the polymers of the present invention can be carried out also by polymerization in aqueous emulsion according to well known methods in the art, in the presence of a radical initiator which can be selected for example from: inorganic peroxides (for example alkaline metal or ammonium persulphates, perphosphates, perborates or percarbonates), optionally in combination with ferrous, cuprous or silver salts, or of other easily oxidizable metals; organic peroxides (for example, disuccinylperoxide, terbutyl-hydroperoxide, diterbutylperoxide); azocompounds (see U.S. Pat. No. 2,515,628 and U.S. Pat. No. 2,520,338, herein incorporated by reference). It is also possible to use organic or inorganic redox systems, such as ammonium persulphate/sodium sulphite, hydrogen peroxide/aminoiminomethansulphinic acid to mentioned just a few.

[0078] In the reaction medium also surfactants of various type are usually present, among which the fluorinated surfactants of formula:

R³ _(f)—X⁻M⁺

[0079] are particularly preferred, wherein R³ _(f) is a C₅-C₆ (per)fluoroalkyl chain or a (per)fluoropolyoxyalkyl chain, X⁻ is —COO⁻ or —SO₃ ⁻, M⁺ is selected from: H⁺, NH₄ ⁺, an alkaline metal ion. Among the most commonly used, ammonium perfluorooctanoate, (per)fluoropolyoxyalkylenes ended with one or more carboxylic groups, etc. can be mentioned.

[0080] During the polymerization, known iodinated a brominated chain transfer agents can be added to the reaction medium. It is also possible to use as chain transfer agents alkaline or earthalkaline metal iodides or bromides, according to U.S. Pat. No. 5,173,553, herein incorporated by reference.

[0081] Other chain transfer agents are mentioned in U.S. Pat. No. 4,766,190, herein incorporated by reference.

[0082] The crosslinking process of the amorphous polymers of the present invention can be carried out according to methods well known in the art. When, for example, one of the comonomers is vinylidene fluoride or vinyl fluoride, curing can be carried out with polyamines or aromatic polyols in the presence of suitable catalysts (accelerants) as described in U.S. Pat. No. 3,876,654, U.S. Pat. No. 4,259,463; when the monomer is perfluorinated, one generally uses in the copolymerization in amounts lower than or equal to 3%, a comonomer having a reactive site formed, for example, by Br, I, CN, OC₆F₅, COOR^(a) wherein R^(a) is an alkyl from 1 to 5 carbon atoms, or by double bonds as described in U.S. Pat. No. 5,268,405; when the polymer contains Br or I, it is cured in the presence of a peroxide or of a polyunsaturated compound as described in U.S. Pat. Nos. 4,948,852, 4,948,853 and 4,983,60, EP 683,149.

[0083] Another object of the present invention consists in the synthesis process of the new (per)fluorovinyl ethers, which comprises the reaction of hypofluorite CF₂(OF)₂ fluorinated olefin of formula R₁, R₂C═CR₃R₄ to give a first intermediate hypofluorite F—CR₁R₂—CR₃R₄—OCF₂OF, the subsequent reaction of said compound with a second fluorinated olefin of formula R₅, R₆C═CR₇R₈ to give second intermediate F—CR₁R₂—CR₃R₄—OCF₂O—CR₅R₆——CR₇R₈—F, which by an elimination reaction such as dehalogenation or dehydrohalogenation leads to the new perfluorovinyl ethers.

[0084] The general scheme of the synthesis is the following:

(a) CF₂(OF)₂+R₁R₂C═CR₃R₄→F—CR₁R₂—CR₃R₄—OCF₂OF  (VI)

(b) F—CR₁R₂—CR₃R₄—OCF₂OF+R₅R₆C²═C¹R₇R₈→F—CR₁R₂—CR₃R₄—OCF₂O—C²R₅R₆—C¹R₇R₈—F  (VII)

dehalogenation./

(c) F—CR₁R₂—CR₃R₄—OCF₂O—C²R₅R₆—C¹R₇R₈—F→,

/dehydrogenation.

CFX═CXOCF₂OR  (I)

[0085] In this synthesis scheme:

[0086] with reference to the formula of the compound (VII):

[0087] R₁, R₄, are the same or different and are H, F; R₂, R₃, are the same or different and are H, Cl under the following conditions: (1) when the final reaction is a dehalogenation, R₂ R₃=Cl; (2) when the final reaction is a dehydrohalogenation one of the two substituents R₂, R₃ is H and the other is Cl;

[0088] R₅, R₆, R₇, R₈ are:

[0089] F, or one of them is a C₁-C₄ linear or branched perfluoroalkyl group, or a C₁-C₄ linear or branched perfluorooxyalkyl group containing from one to three oxygen atoms, or R₅ and R₇, or R₆ and R₈, are linked each other to form with C² and C¹ a C₅-C₆ cycle perfluoroalkyl group;

[0090] when one of the R₅ to R₈ radicals is a C₂-C₄ linear or branched fluoroalkyl, or a C₂-C₄ linear or branched fluorooxyalkyl group containing from one to three oxygen atoms, one or two of the other R₅ to R₈ are F and one or two of the remainders, equal to or different from each other, are selected from H, Cl, Br, Iodine; when the substituents selected from H, Cl, Br, Iodine are two, they are both linked to the same carbon atom; when R₅ and R₇, or R₆ and R₈, are linked each other to form with C² and C¹ a C₅-C₆ cycle fluoroalkyl group, one of the two free substituents R₆, R₈ or R₅, R₇ is F and the other is selected from H, Cl, Br, Iodine.

[0091] the fluoroalkene used in the reaction a) is replaceable with that of the subsequent reaction b); in this case the meanings defined for the substituents of the R₁-R₄ group, and respectively of the R₅-R₈, group, are interchangeable each other, with the proviso that the position of each radical of each of the two groups R₁-R₄ and R₅-R₈ with respect to —OCF₂O— on the chain of the intermediate compound (VII), is the same which is occupied if the synthesis takes place according to the above reported scheme and the two olefins each react in the considered steps.

[0092] In the first reaction a) of the above illustrated scheme a hypofluorite gas flow CF₂(OF)₂, optionally suitably diluted with an inert fluid, comes into contact (i.e is contacted with), in a suitable reactor with outlet, on the bottom of the same (first reactor), with the R₁R₂C═CR₃R₄ olefin, optionally diluted in an inert fluid and preferrably in gas flow, to allow the chemical reaction a) with formation of the intermediate hypofluorite (VI). To favour the reaction stoichiometry, the reactants must be introduced into the reactor in an approximately unitary molar ratio, or with an excess of CF₂(OF)₂. The residence time of the mixture in the reactor can range from about a few hundredths of second up to about 120 seconds depending on the olefin reactivity, the reaction temperature, and the presence of optional reaction solvents.

[0093] The reaction temperature can range from about −40° to about −150° C., preferably from about −80° to about −130° C.

[0094] The compound (VI) usually is not separated from the reaction product and it is transferred in a continuous way to the subsequent reaction described in step b).

[0095] The mixture of the products coming out from the first reactor can be heated at room temperature before being fed into the second reactor.

[0096] In the second reaction b), the second olefin R₅R₆C═CR₇R₈ pure or in solution, reacts with the product obtained in the first reaction with formation of compound (VII).

[0097] The olefin can be fed in a continuous way, so as to maintain its concentration constant in the reactor; except for normal variation as would be expected by the skilled asrtisan. The temperature of the reaction b) can range from about −20° to about −130° C., preferably from about −50° to about −100° C. The olefin concentration is higher than or equal to about 0.01M, preferably the concentration is higher than 3M, more preferably also the compound in a highly purified state can be used.

[0098] The solvents used in steps a) and b) are perfluorinated or chlorohydrofluorinated solvents or hydrofluorocarbons. Examples of said solvents are:

[0099] CF₂Cl₂, CFCl₃, CF₃CFH₂, CF₃CF₂CF₃, CF₃CCl₂H, CF₃CF₂Cl.

[0100] In the reaction c) the compound (VII), dependently on the olefins used in steps a) and b), after distillation from the reaction product, is subjected to dechlorination or to dehydrochlorination to obtain the vinyl ethers of formula (I). This last step can be carried out by using reactions widely described in the prior art. The suitable selection of the substituents R₁ to R₈ in the two olefins used in the synthesis allows to obtain the vinyl ethers of the present invention.

[0101] Another object of the invention is a process wherein a hypofluorite of formula X₁X₂C(OF)₂ wherein X₁ and X₂ equal or different are F, CF₃, and two fluoroalkenes of formula respectively R^(A) ₁R^(A) ₂C═CR^(A) ₃R^(A) ₄ and R^(A) ₅R^(A) ₆C═CR^(A) ₇R^(A) ₈, wherein R^(A) ₁-R^(A) ₈ equal or different, are F, H, Cl, Br, I, —CF₂OSO₂F, —SO₂F,—C(O)F, C₁-C₅ linear or branched perfluoroalkyl or oxyperfluoroalkyl group, are reacted according to steps a) and b), excluding the dehalogenation or dehydrohalogenation step, to obtain compounds of general formula (VIII)

F—CR^(A) ₁R^(A) ₂—CR^(A) ₃R^(A) ₄—OCF₂O—CR^(A) ₅R^(A) ₆—CR^(A) ₇R^(A) ₈—F.

[0102] The following Examples are reported with the purpose to illustrate the invention and they do not limit the scope of the same.

[0103] In the Examples the thermogravimetric analysis TGA is carried out by using a 10° C./min rate.

EXAMPLE 1

[0104] Synthesis of CF₃CF₂OCF₂OCFClCF₂Cl perfluoro-1-2,dichloro-3,5-dioxaheptane.

[0105] The reactor used is of the cylindrical type, with a total volume of about 300 ml and is equipped with magnetic dragging mechanical stirrer, turbine with recycle of the reacting gas placed at 20 cm from the reactor top, internal thermocouple, two internal copper pipes for the reactant feeding which end at about 1 mm from the turbine, and product outlet from the bottom. In the reactor, inside of which the temperature is maintained at −114° C., 1.1 1/h (liters/hour) of CF₂(OF)₂ and 3.3 l/h of He are introduced through one of the two inlet pipes; A flow of 1.1 l/h of CF₂═CF₂ and 0.7 l/h of He is maintained through the second inlet pipe. Feeding is continued for 6.6 hours.

[0106] The residence time of the transport gas in the reaction zone comprised between the outlet of the two feeding pipes in the reactor and the inlet of the discharge pipe is of about 4 sec.

[0107] On the reactor bottom the reaction products are brought

[0108] The reactor used is of the cylindrical type, with a total volume of about 300 ml and is equipped with magnetic dragging mechanical stirrer, turbine with recycle of the reacting gas placed at 20 cm from the reactor top, internal thermocouple, two internal copper pipes for the reactant feeding which end at about 1 mm from the turbine, and product outlet from the bottom. In the reactor, inside of which the temperature is maintained at −114° C., 1.1 l/h (liters/hour) of CF₂(OF)₂ and 3.3 l/h of He are introduced through one of the two inlet pipes; A flow of 1.1 l/h of CF₂=CF₂ and 0.7 1/h of He is maintained through the second inlet pipe. Feeding is continued for 6.6 hours.

[0109] The residence time of the transport gas in the reaction zone comprised between the outlet of the two feeding pipes in the reactor and the inlet of the discharge pipe is of about 4 sec.

[0110] On the reactor bottom the reaction products are brought to room temperature and the gaseous mixture flow, monitored by gas chromatography, is fed in a continuous way, under mechanical stirring, into a second reactor having a 250 ml volume maintained at the temperature of −70° C., equipped with mechanical stirrer, thermocouple, dipping inlet for the reacting mixture, outlet with head of inert gas. The reactor contains 72.6 g of dichlorodifluoroethylene CFCl═CFCl.

[0111] At the end of the addition of reacting gases into the second reactor, the reaction raw material is distilled by a plate column at atmospheric pressure, collecting 41.5 g of the desired product (boiling point 91° C.).

[0112] The yield of perfluoro-1,2 dichloro-3,5-dioxaheptane, calculated with respect to CF₂(OF)₂, is of 36%.

[0113] Characterization of perfluoro 1,2, dichloro-3,5-dioxaheptane.

[0114] Boiling point at atmospheric pressure: 91° C.

[0115]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃at 0): CF₂═CF—OCF₃ and 0.7 l/h of He for 4.5 hours.

[0116] The residence time of the transport gas in the reaction zone comprised between the reactor outlet and the end of the two feeding pipes is of about 3 sec.

[0117] On the reactor bottom the reaction products are brought to room temperature and the gaseous mixture flow, monitored by gas chromatography, is fed in a continuous way, under mechanical stirring, into a second reactor identical to the one used for the same step in Example 1. Inside, where a temperature of −70° C. is maintained, there are 51 g of dichlorofluoroethylene CFCl═CFCl.

[0118] At the end of the addition of the reacting gases into the second reactor, the reaction raw material is distilled by a plate column at the reduced pressure of 250 mmHg. 50 g of a mixture formed by two isomers, respectively, isomer A) perfluoro-1,2-dichloro-3,5,8-trioxanonane and isomer 3) perfluoro-1,2-dichloro-3,5,7-trioxa-6-methyloctane are collected. The mixture composition is determined by gas chromatography and is the following: isomer A 79%, isomer B 21%. The molar yield of A+B with respect to the used CF₂(OF)₂ is 38%. The molar yield of A+B with respect to the used perfluoromethylvinylether is 42%. The isomers have been separated by preparative gas chromatography.

[0119] Characterization of Products A and B

[0120] Mixture boiling point (A 79%, B 21%) at the reduced pressure of 250 mmHg: 82° C.

[0121]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer A: −50.6/−52.4 (2F, O—CF₂−O); −70.0/−71.8 (2F, C—CF₂Cl); −77.7 (1F, O—CFCl—C); −55.3/−55.6 (3F, CF₃—OC); −90.7/−91.1 (2F, C—OCF₂—C); −90.2/−90.6 (2F, C—OC—CF₂OCOC).

[0122]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of isomer B: −50.0/−52.1 (2F, O—CF₂—O;) −70.0/−71.8 (2F, C—CF₂Cl); −77.9 (1F, O—CFCl—C); −54.6/−54.9 (3F, CF₃OC); −85.7/−86.1 (3F, OC (CF₃)O); −100.3/−101.0 (1F, OCF(C)O).

[0123] Mass spectrum (electronic impact) main peaks and respective intensities:

[0124] Product A: 69 (50); 119 (100); 151 (50); 185 (42); 251 (38);

[0125] Product B: 69 (96); 97 (50); 135 (42); 151 (92); 185 (100).

[0126] IR spectrum (cm⁻¹), intensity of the mixture A 79%, B 21%: (w)=weak, (m)=medium, (s)=strong, (vs)=very strong: 1388 (w); 1288 (vs); 1233 (vs); 1151 (vs); 1104 (vs); 1032 (s); 846 (m); 685 (w)

EXAMPLE 3

[0127] Synthesis of CF₃OCF₂CF₂OCF₂OCHClCHFCl perfluoro-1,2-dichloro-1,2-dihydro-3,5,8-trioxanonane (isomer C) and CF₃OCF (CF₃) OCF₂OCHClCHFC1 perfluoro-1,2-dichloro-1,2-dihydro-3,5,7-trioxa-6-methyloctane (isomer D).

[0128] In a reactor identical to that used in Example 1, maintained at the temperature of −112° C., 1.55 l/h of CF₂(OF)₂ and 4.5 l/h of He are introduced through one of the two inlet pipes; through the second inlet pipe 1.4 l/h of CF₂═CF—OCF₃ and 0.7 l/h of He for 5 hours.

[0129] The residence time of the transport gas in the reaction zone comprised between the reactor outlet and the end of the two feeding pipes is about 3 sec.

[0130] On the reactor bottom the reaction products are brought to room temperature and the gaseous mixture flow, monitored by gas chromatography, is fed in a continuous way, under mechanical stirring, into a second reactor identical to the one used for the same step in Example 1. Inside, the temperature is of −70° C. and there are 50 g of 1,2-dichloroethylene CClH═CClH and 50 g of CFCl₃.

[0131] At the end of the addition of the reacting gases into the second reactor, after distillation of the solvent at room pressure, the reaction raw material is distilled by a plate column at the reduced pressure of 100 mmHg. 43.5 g of the mixture of the desired products (isomer C 78%, isomer D 22W, determined by gaschromaography) are collected. The molar yield of C+D with respect to the used CF₂(OF)₂ is 33%. The isomers have been separated by preparative gas chromatography.

[0132] Characterization of Products C and D

[0133] Mixture boiling point (C 78%, D 22%) at the reduced pressure of 100 mmHg: 71° C.

[0134]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer C perfluoro-1,2-dichloro-1,2-dihydro-3,5,8-trioxanonane: −56.0/−57.2 (2F, O—CF₂—O); −143.2/−146.0 (1F, C—CHFCl); −55.8 (3F, CF₃—OC); −91.0/−91.4 (2F, C—OCF₂—C); −90.3/−90.5 (2F, C—OC—CF₂OCOC).

[0135]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer D perfluoro-1,2-dichloro-1,2-dihydro-3,5,7-trioxa-6-methyloctane: −56.01−57.2 (2F, O—CF₂—O); −143.2/−146.0 (1F, C—CHFCl) −54.9/−55.1 (3F, CF₃—OC); −86.21−86.3 (3F, OC(CF₃)O); −100.5/−101.0 (1F, OCF(C)O).

[0136]¹H spectrum in p.p.m. (with respect to TMS) of the isomers C and D: 6.28/6.05 (1H—CHFCl); 6.02/5.95 (1H—CHCl—)

[0137] Mass spectrum (electronic impact), main peaks and respective intensities %: 69 (84); 119 (100); 185 (51.1); 251 (84); 281 (15.8); 283 (4.8); 347 (5.7); 349 (1.7).

[0138] IR spectrum (cm⁻¹) intensity : (w)=weak, (m)=medium, (s)=strong, (vs)=very strong: 3001.0 (w); 2920.9 (w); 2850.9 (w); 1286.3 (vs); 1233.7 (vs); 1125.5 (vs); 1081.8 (s); 1047.9 (s); 815.9 (m); 766.3 (m).

EXAMPLE 4

[0139] Dehalogenation of perfluoro 1,2-dichloro-3,5-dioxaheptane

[0140] In a 25 ml three-necked flask, equipped with mechanical stirrer, thermometer, dropping funnel, distillation column equipped with water refrigerant and collecting trap maintained at −78° C. and connected to a mechanical vacuum pump, 150 ml of DMF, 15 g of poudered Zn in powder, 0.5 g of K₂CO₃ and 100 mg of I₂ are introduced. The internal temperature is brought to 80° C. and 50 g of perfluoro -1,2-dichloro-3,5-dioxaheptane are added dropwise. When the addition is over the mixture is allowed to react for about 30 minutes. At the end the internal pressure gradually brought from starting 760 mmHg to 300 mmHg. After about 20 minutes the collecting trap containing 34.2 g of perfluoro-3,5-dioxa-1-heptene (MOVE 1) is disconnected.

[0141] The dehalogenation yield is 85%.

[0142] Characterization of perfluoro-3,5-dioxa-1-heptene (MOVE 1)

[0143] Boiling point at atmospheric pressure: 41.9° C.

[0144]¹⁹F-NMR spectrum in p.p.m. with respect to CFCl₃ at 0: −56.8 (2F, O—CF₂—O); −87.2 (3F, CF₃—C); −90.6 (2F, C—CF₂—O); −114 (1F, O—C═C—F); −121.8 (1F, O—C═CF); −137 (1F, O—C—F═C);

[0145] Mass spectrum (electronic impact), main peaks and respective intensities: 69 (66.5%); 119 (100%); 147 (83.4%); 185 (89.4%); 216 (67.3%); 282 (8.2%).

[0146] IR spectrum (cm⁻¹) intensity: (w)=weak, (m)=medium, (s)=strong, (vs)=very strong: 1839.5 (m); 1407.6 (w); 1307.4 (vs); 1245.8 (vs); 1117.4 (vs); 907.2 (m); 846.0 (m)

EXAMPLE 5

[0147] Dehalogenation of the Isomer Mixture A+B Obtained in Example 2 (perfluoro-1,2-dichloro-3,5,8-trioxanonane CF₃OCF₂CF₂CF2OCFClCF₂Cl+perfluoro-1,2-dichloro-3,5,7-trioxa-6-methyloctane CF₂OCF (CF₃) OCF₂OCFClCF₂Cl).

[0148] In a 250 ml flask equipped as described in the previous Example 4, 110 ml of DMF, 10 g of Zn in powder and 0.3 ml of Br₂ are introduced. The internal temperature is brought to 75° C. and 30.3 g of the binary mixture A+B separated in the previous Example 2 are added drop by drop. when the addition is over the mixture is allowed to ract for about 3 hours. At the end the internal pressure is gradually lowered from 760 mmHg to 200 mmHg at −79° C. After about 30 minutes the collecting trap is disconnected. The corresponding content, which is washed with water, is recovered. At the end 24.0 g of a mixture formed for 79% (gas chromatographic determination) by perfluoro-3,5,8-trioxa-l-nonene (MOVE '2) CF₃OCF₂CF₂OCF₂OCF═CF₂ (isomer A′) and for 21% by perfluoro-3,5,7-trioxa-6,methyl-1 octene (MOVE 2a) CF₃OCF(CF₃)OCF₂O—CF═CF₂ (isomer B′) are obtained, which are then separated by preparative gas chromatography.

[0149] Characterization of products A′ and B′

[0150] Boiling range of the isomer mixture at atmospheric pressure: 72.5⁰-74.5° C.

[0151]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer A′: −55.9 (3F, CF₃-0); −56.9 (2F, O—CF₂—O); −90.8 (2F, C—CF₂—O) −91.2 (2F, O—CF₂—C); −114 (1F, O—C═C—F); −121.8 (1F, —O—C═CF) −137 (1F, O—CF═C)

[0152]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer B′: −55.9 (3F, CF₃-0); −56.2 (2F, O—CF₂—O); −86.4 (3F, CF₃—C) −100.9 (1F, CF; −114 (1F, O—C═C—F); −122 (1F, O—C═CF); −137 (1F, O—CF═C).

[0153] Mass spectrum (electronic impact), main peaks and respective intensities of the isomer A′: 69 (74); 81 (18); 119 (100); 147 (59); 185 (26); 251 (21);

[0154] Mass spectrum (electronic impact), main peaks and respective intensities of the isomer B′: 69 (80); 81 (37); 97 (47); 119 (36); 147 (100); 185 (19).

[0155] IR spectrum (cm⁻¹) intensity: (w)=weak, (m)=medium, (s)=strong, (vs)=very strong, 1839 (m); 1343 (s); 1248 (vs); 1145 (vs); 918 (m); 889 (m).

EXAMPLE 6

[0156] Dehalogenation of the Isomers C+D Mixture Obtained in Example 3 (CF3OCF₂CF₂OCF₂OCHClCHFCl perfluoro-1,2-dichloro-1,2-dihydro-3,5,8-trioxanonane (isomer C)+CF₃OCF(CF₃) OCF₂OCHClCHFCl perfluoro-1,2-dichloro-1,2-dihydro-3,5,7-trioxa-6-methyloctane (isomer D)).

[0157] In a 500 ml three-necked flask, equipped with mechanical stirrer, thermometer, dropping funnel, distillation column having a water refrigerant and a collecting trap maintained at the temperature of −78° C., 250 ml of DMF, 30 g of zinc in powder and 300 mg of I₂ are introduced.

[0158] The temperature is brought to 100° C. and 56.9 g of the isomer mixture obtained in Example 3 are added dropwise.

[0159] When the addition is over the reactor internal temperature is brought to 120° C. and stirring is maintained for 24 hours. At the end the reaction product, which contains traces of solvent and which is collected in the trap maintained at −78° C., is distilled. After washing with water 35 g of a mixture of perfluoro-1,2-dihydro-3-5-8-trioxa-1-nonene (isomer C′, 79% by moles) and of perfluoro-1,2-dihydro-3-5-7-trioxa-5-methyl-1-octene (isomer-D′, 21% by moles) are recovered. The isomers are separated by preparative gas chromatography.

[0160] The dehaloagenation reaction yield is 76%.

[0161] Characterization of products C′ and D′

[0162] Boiling range of the mixture of isomers C′ 79%, D′ 21% at atmospheric pressure: 90.0°-92.0° C.

[0163]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer C′ perfluoro-1,2-dihydro-3,5,8-trioxa-1-nonene: −55.7 (3F, CF₃—O); −57.3 (2F, O—CF₂—O); −90.9 (2F, C—CF₂—O); −91.2 (2F, O—CF₂—C); −149.31/−150.0 (1F, O—C═C—F).

[0164]¹⁹F-NMR spectrum in p.p.m. (with respect to CFCl₃ at 0) of the isomer D′ perfluoro-1,2-dihydro-3,5,7-trioxa-6-methyl-1-octene: −55.0 (3F, CF₃—O); −56.9 (2F, O—CF₂—O); −86.2 (3F, CF₃—C); −101.0 (1F, CF). −149.3/−150,0 (1F, O—C═C—F)

[0165] Mass spectrum (electronic impact), main peaks and respective intensities %: 69 (82); 119 (100); 185 (29); 246 (25); 251 (20); 312 (43).

[0166] IR spectrum (cm⁻¹) intensity of the isomer mixture (C′ 79%, D′ 21%): (w)=weak, (m)=medium, (s)=strong, (vs)=very strong: 3140 (w); 1722 (w); 1695 (w); 1402 (m); 1281 (vs); 1237 (vs); 1147 (vs); 1106 (vs); 1030 (m).

EXAMPLE 7

[0167] Homopolymerization of perfluoro-3,5-dioxa-1-heptene (MOVE 1).

[0168] In a glass reactor for polymerizations, having a 20 ml volume, equipped with magnetic stirrer and with an inlet for the reactant feeding and discharge, 60 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl and 3 g of MOVE 1 are in sequence introduced. The so charged reactor is brought to the temperature of −196° C., evacuated, brought to room temperature. The cooling-evacuation procedure is repeated. At the end of the degassing operations the reactor is thermostated at the temperature of 30° C. and the mixture is allowed to react under these conditions for two days under magnetic stirring.

[0169] The reaction raw material which is finally recovered appears as a slightly viscous, transparent, colourless and homogeneous solution.

[0170] After distillation of the unreacted monomer, and subsequent stripping under vacuum at 150° C. for 3 hours, 180 mg of the polymer are separated.

[0171] The IR analysis of the obtained polymer shows that, in the spectrum, absorption bands in the zone of the fluorinated double bonds are absent.

[0172] The ¹⁹F-NMR analysis carried out on the polymer dissolved in C₆F₆ is in accordance with the homopolymer structure having a molecular weight of 50,000. The analysis does not show the presence of unreacted monomer.

[0173] The DSC thermogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The polymer T_(g), determined by DSC, is −35.4° C. The thermogravimetric analysis (TGA) shows a weight loss of 2% at 332° C. and of 10% at 383° C.

EXAMPLE 8

[0174] Copolymer between perfluoro-3,5,8-trioxa-1-nonene CF₃OCF₂CF₂OCF₂OCF═CF₂ (MOVE 2) and perfluoro-3,5,7-trioxa-6,methyl-1-octene CF₃OCF(CF₃)OCF₂O—CF═CF₂ (MOVE 2a)

[0175] In a reactor having the same characteristics as that described in Example 7, 150 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl and 3.2 g of a mixture prepared according to the process of Example 5 and containing 83% MOVE 2 and 17% MOVE 2a, are introduced. The reactor is then evacuated, cooled, and the subsequent reaction carried out as described in the previous Example 7.

[0176] The reaction raw material appears as a slightly viscous, transparent, colourless and homogeneous solution. The monomers which have not reacted are distilled and a stripping under vacuum at 150° C. for 3 hours is in sequence carried out. Finally 350 mg of the polymer are separated.

[0177] The IR analysis shows that, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds are absent.

[0178] The ¹⁹F-NMR analysis is in accorddnce with the copolymer structure having an average molecular weight of 35,000 and a MOVE 2/MOVE 2a content equal to the percentages of the reacting mixture; unreacted monomers are not evident.

[0179] The DSC thermogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The polymer T_(g), determined by DSC, is −52.6° C. The thermogravimetric analysis (TGA) shows a weight loss of 2% at 280° C. and of 10% at 327° C.

EXAMPLE 9

[0180] Crystalline Copolymer between MOVE 1 and TFE.

[0181] A 5 l steel AISI 316 autoclave with stirrer working at 650 rpm has been used. After the vacuum has been effected, 3 l of demineralized water, 15.70 g of MOVE 1 and the microemulsion prepared according to the procedure described in U.S. Pat. No. 4,864,006 are in sequence introduced, so as to have a concentration of 2 g of surfactant/l of water.

[0182] The autoclave is heated up to 75° C. and then 0.32 bar of ethane are introduced. A gaseous mixture in a molar ratio of 54.55 TFE/MOVE 1 is pumped by a compressor until having inside the autoclave a pressure of 21 absolute bar.

[0183] The composition of the gaseous mixture present in the autoclave top is analyzed by gas chromatography.

[0184] Before the reaction starting the gaseous phase results to be formed by the following molar percentages of the reactants: 93.1% TFE, 5.5% MOVE 1 and 1.4% Ethane. The reaction is triggered by feeding in a continuous way by a metering pump a potassium persulphate 0.0031 molar solution at a flow rate of 88 ml/h.

[0185] The pressure is maintained constant by feeding the monomer mixture. The polymer synthesis is stopped after 742 g of mixture have been fed in total.

[0186] The reactor is cooled at room temperature, the emulsion is discharged and the coagulation is induced by HNO₃ (65%) addition.

[0187] The polymer is separated, washed with water and dried at 220° C.

[0188] The IR analysis shows the presence of very small absorption bands in the carboxyl zone, whose intensity results to be half of the one obtained from a TFE/PVE copolymer film having the same thickness, prepared according to the comparative Example 3. MFI according to ASTMD 1238-52T was 4.4. The polymer therefore results thermally more stable (see the comparative Example hereunder).

EXAMPLE 10

[0189] Amorphous Copolymer between MOVE 1 and TFE.

[0190] In an AISI-316 polymerization reactor having a 40 ml volume, equipped with magnetic stirring, pressure transducer and an inlet for the reactant feeding and discharge, 250 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl, 9.8 mmoles of MOVE 1 and 18 mmoles of tetrafluoroethylene are introduced.

[0191] The reactor is cooled to the temperature of −196° C., evacuated, then brought to room temperature. The procedure and cooled as repeated twice.

[0192] At the end of the degassing operations the reactor is thermostated at the temperature of 30° C. and the reaction mixture maintained under magnetic stirring. The internal pressure decreases from 6.4 atm to 4.7 atm in about 8 hours (reaction time).

[0193] After distillation of the unreacted monomers and polymer stripping under vacuum for 3 hours at 150° C., 1,100 mg of polymer are recovered. The polymer appears as a transparent and colourless rubber.

[0194] By ¹⁹F-NMR analysis of the polymer dissolved under heating in C₆F₆ it is determined that the MOVE 1 molar percentage in the polymer is 24%.

[0195] The IR analysis does not show, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds, and shows the presence of very small absorption bands in the zone of the carboxyl signals. The intensity of these signals, compared with the similar ones obtained from a film having the same thickness obtained with the polymer of the comparative Example 1, is equal to about {fraction (1/10)} of the latter.

[0196] The DSC thermogram does not show any melting endotherm, wherefore the polymer is amorphous. The T_(g) determined by DSC is −21.4° C.

[0197] The TGA shows a weight loss of 2% at 450° C. and of 10% at 477° C. The polymer therefore results thermally more stable (see the comparative Example hereunder) with respect to the comparative Example (see below).

[0198] The polymer intrinsic viscosity measured at 30° C. in Fluorinert® FC-75, is 35.5 ml/g.

EXAMPLE 11

[0199] Amorphous Copolymer between MOVE 1 and TFE.

[0200] In an AISI-316 polymerization reactor identical to that described in the previous Example 10, 250 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl, 9.75 mmoles of MOVE 1 and 9 mmoles of tetrafluoroethylene are introduced in sequence.

[0201] The procedure already described in the previous Example 10 is followed until the thermostating step at the temperature of 30° C. under magnetic stirring. During the reaction the internal pressure decreases from 3.4 atm to 2.9 atm in about 8 hours.

[0202] At the end the unreacted monomers are distilled and the polymer is stripped under vacuum at 150° C. for 3 hours.

[0203] 480 mg of the polymer are separated.

[0204] By ¹⁹F-NMR analysis of the polymer dissolved under heating in C₆F₆ it is determined that the MOVE 1 molar percentage in the polymer is 39%.

[0205] The IR analysis shows that, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds are absent.

[0206] The DSC thermogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The T_(g) determined by DSC is −29.8° C.

[0207] The TGA shows a weight loss of 10% at 435° C.

EXAMPLE 12

[0208] Amorphous Copolymer between MOVE 1 and CF₂═CH₂

[0209] In a polymerization reactor identical to that described in Example 10, 250 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl, 10 mmoles of MOVE 1, and 18 mmoles of VDF are introduced in sequence.

[0210] The procedure already described in the previous Example 10 is followed until the thermostating step at the temperature of 30° C. under magnetic stirring. The internal pressure decreases from 6.8 atm to 5.0 atm during the reaction (about 8 hours).

[0211] After distillation of the unreacted monomers and subsequent polymer stripping under vacuum at 150° C. for 3 hours, 1,600 mg of the polymer are separated, appearing as a transparent and colourless rubber.

[0212] By the ¹⁹F-NMR analysis carried out on the polymer dissolved in C₆F₆, it is determined that the MOVE 1 molar percentage in the polymer is 40%.

[0213] The DSC termogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The T_(g) determined by DSC, is −47° C.

[0214] The TGA shows a weight loss of 2% at 428° C. and of 10% at 455° C.

EXAMPLE 13

[0215] Amorphous Terpolymer MOVE 2/MOVE 2a/TFE.

[0216] In a polymerization reactor identical to that described in Example 10, 100 μl of perfluoropropionylperoxide at 6% by weight in CFCl₂CF₂Cl, 10 mmoles of a MOVE 2 (83%) and MOVE 2a (17%) mixture synthetized according to the process of Example 5, and 18 mmoles of tetrafluoroethylene (TFE) are in sequentially introduced.

[0217] The procedure already described in the previous Example 10 is then followed until thermostating at the temperature of 30° C. under magnetic stirring. The internal pressure decreases from 6.1 atm to 3.9 atm during the reaction (about 8 hours).

[0218] After distillation of the unreacted monomers and polymer stripping under vacuum at 150° C. for 3 hours, 1,131 mg of the polymer are separated.

[0219] By the ¹⁹F-NMR analysis carried out on the polymer dissolved in C₆F₆ it results that the total molar percentage of the MOVE 2+MOVE 2a perfluorovinyl ethers units in the polymer is 22%; the MOVE 2/MOVE 2a ratio by moles in the polymer is 83/17 and it is equal to that of the starting feed mixture.

[0220] The presence of unreacted monomers is not evident.

[0221] The IR analysis does not show, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds, and it shows the presence of very small absorption bands in the zone of the carboxyl signals. The intensity of these signals, compared with the similar ones obtained from a film having the same thickness obtained with the polymer of the comparative Example 1, is equal to about {fraction (1/10)} of the latter.

[0222] The DSC thermogram does not show any melting endotherm, wherefore the polymer is amorphous. The T_(g) determined by DSC, is −37.5° C.

[0223] The TGA shows a weight loss of 10% at 473° C.

[0224] The polymer intrinsic viscosity measured at 30° C. in Fluorinert® FC-75, is 40.0 ml/g.

EXAMPLE 14

[0225] Amorphous Terpolymer MOVE 2/MOVE 2a/TFE.

[0226] In a polymerization reactor identical to that described in Example 10, 100 μl of perfluoropropionylperoxide at 6% by weight in CFCl₂CF₂Cl, 9.7 mmoles of the MOVE 2 (83%) and MOVE 2a (17%) mixture synthesized according to the process of Example 5, and 10 mmoles of tetrafluoroethylene (TFE) are in sequence introduced.

[0227] The procedure already described in the previous Example 10 is then followed until the thermostating step at the temperature of 30° C. under magnetic stirring. The internal pressure decreases from 3.6 atm to 2.7 atm during the course of reaction (about 8 hours).

[0228] After distillation of the unreacted monomers and polymer stripping under vacuum at 150° C. for 3 hours, 652 mg of polymer are separated.

[0229] By the ¹⁹F-NMR analysis carried out on the polymer dissolved in C₆F₆ it results that the total molar percentage of units derived from the MOVE 2+MOVE 2a perfluorovinyl ethers in the polymer is 37%; the MOVE 2/MOVE 2a molar ratio in the polymer is 83/17 and it is equal to that of the starting feed mixture.

[0230] The presence of unreacted monomers is not evident.

[0231] The IR analysis does not show, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds.

[0232] The DSC thermogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The T_(g) determined by DSC, is −44.5° C.

[0233] The TGA shows a weight loss of 10% at 451° C.

[0234] The polymer intrinsic viscosity measured at 30° C. in Fluorinert® FC-75, is 16.7 ml/g.

EXAMPLE 15

[0235] Amorphous Copolymer between perfluoro-1,2-dihydro-3,5,8-trioxa-1-nonene (H-MOVE 2) and perfluoro-1,2-dihydro-3,5,7-trioxa-6-methyl-1-octene (H-MOVE 2a) with molar ratio 88/12.

[0236] In a reactor identical to that described in Example 7, 200 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂—CF₂Cl and 3.1 g of an 88/12 H-MOVE 2/H-MOVE 2a 88/12 mixture are introduced.

[0237] The procedure described in Example 7 is followed.

[0238] The recovered reaction raw material appears as a slightly viscous, transparent, colourless and homogeneous solution.

[0239] After distillation of the unreacted monomer and subsequent stripping under vacuum at 150° C. for 3 hours, 120 mg of polymer are separated.

[0240] The IR analysis of the obtained polymer shows that, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds are absent.

[0241] The ¹⁹F-NMR analysis is in accordance with the copolymer structure having a content of monomers H-MOVE 2 and H-MOVE 2a equal to the H-MOVE 2 and H-MOVE 2a percentages in the reacting mixture. The analysis does not show the presence of unreacted monomers.

[0242] The DSC thermogram does not show any melting endotherm, wherefore the polymer is amorphous. The polymer T_(g) determined by DSC, is −58.0° C. The thermogravimetric analysis (TGA) shows a weight loss of 10% at 307° C.

EXAMPLE 16

[0243] Terpolymer H-MOVE 2/H-MOVE 2a/TFE.

[0244] In a reactor similar to that described in Example 10, 100 μl of perfluoropropionylperoxide at 6% by weight in CFCl₂—CF₂Cl and 5 mmoles of a H-MOVE 2 (88%) and H-MOVE 2a (12%) mixture and 18 mmoles of tetrafluoroethylene, are introduced.

[0245] The same procedure described in Example 10 is followed.

[0246] At the end of the degassing, the reactor is thermostated at the temperature of 30° C. under magnetic stirring. The internal pressure decreases from 6.8 atm to 6.5 atm in about 6 hours (reaction time).

[0247] After distillation of the unreacted monomers and polymer stripping under vacuum at 150° C. for 3 hours, 300 mg of the polymer are separated.

[0248] By ¹⁹F-NMR analysis of the polymer dissolved under heating in C₆F₆ it is calculated that the molar percentage (mole %) of units derived from the perfluorovinyl ethers (H-MOVE 2+H-MOVE 2a) contained in the polymer is 33%. The H-MOVE 2/H-MOVE 2a molar ratio in the polymer is equal to the H-MOVE 2/H-MOVE 2a molar ratio of the feed mixture. Unreacted monomers are not evident.

[0249] The IR analysis does not show, in the polymer spectrum, absorption bands in the zone of the fluorinated double bonds.

[0250] The DSC thermogram does not show any melting endotherm, wherefore the polymer is amorphous. The Tg determined by DSC, is −44.5° C.

[0251] The TGA shows a weight loss of 10% at 450° C.

EXAMPLE 1 (COMPARATIVE)

[0252] Copolymer PVE/TFE.

[0253] In a polymerization reactor identical to that described in Example 10, 250 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂CF₂Cl, 9.8 mmoles of PVE and 18 mmoles of tetrafluoroethylene, are in sequence introduced.

[0254] The procedure already described in the previous Example 10 is followed until thermostating at the temperature of 30° C. under magnetic stirring. The reaction time is eight hours.

[0255] After distillation of the unreacted monomers and stripping under vacuum at 150° C. for 3 hours, 540 mg of the polymer are recovered.

[0256] By the ¹⁹F-NMR analysis carried out on the polymer dissolved in C₆F₆ it is calculated that the PVE molar percentage in the polymer is 23%.

[0257] The IR analysis shows that, in the polymer spectrum, there are absorption bands in the carboxyl zone, whose intensity is 10 times higher than that obtained from a MOVE 1/TFE copolymer film prepared according to Example 10, and having the same thickness.

[0258] The DSC thermogram does not show any melting endothermic curve, wherefore the polymer is amorphous. The TGA shows a weight loss of 2% at 427° C. and of 10% at 463° C. The Tg, determined by DSC, is +15° C.

[0259] The polymer intrinsic viscosity, measured at 30° C. in Fluorinert® FC-75, is 51 ml/g.

EXAMPLE 2 (COMPARATIVE)

[0260] Copolymer between β-PDE (CF₃OCF₂CF₂OCF═CF₂)/TFE.

[0261] In a polymerization reactor identical to that described in Example 10, 250 μl of perfluoropropionylperoxide at 3% by weight in CFCl₂—CF₂Cl, 10 mmoles of β-PDE, and 18 mmoles of tetrafluoroethylene, are in sequence introduced.

[0262] The procedure described in the previous Example 10 is followed until the thermostating step at the temperature of 30° C. under magnetic stirring.

[0263] By the ¹⁹F-NMR analysis carried out on the polymer purified of monomers by the processes described in the previous Examples, it is calculated that the molar percentage of β-PDE in the polymer is 23%.

[0264] The DSC thermogram does not show any melting endothermic curve wherefore the polymer is amorphous. The T_(g), determined by DSC, is −4.8° C.

[0265] This Tg value is clearly higher than those obtainable with the vinyl ethers of the invention (see the above Examples).

EXAMPLE 3 (COMPARATIVE)

[0266] Crystalline Copolymer PVE/TFE (PFA).

[0267] One operates as in Example 9 except that in this case the perfluoropropylvinyl ether (PVE) is used instead of α-PDE to obtain a copolymer having MFI equal to that of the Example copolymer of 9.

[0268] The IR analysis shows absorption bands in the carboxyl zone, the intensity is of which double those obtained for a TFE/MOVE 1 copolymer film of equal thickness and prepared according to Example 9. 

I claim:
 1. A fluorovinyl ether of formula: CFX═CXOCF₂OR  (I) wherein: 1) R is a C₂-C₆ linear or branched perfluoroalkyl group, a C₅-C₆ cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms; 2) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be replaced with atoms selected from the group consisting of H, Cl, Br, and I; and 3) X is F or H.
 2. The fluorovinyl ether of claim 1 wherein R is CF₂CF₂Y and Y is F or OCF₃.
 3. The fluorovinyl ether of claim 2 wherein each X is F.
 4. The fluorovinyl ether of claim 3 wherein Y is F.
 5. A polymer obtained by the polymerization, alone or in combination with one or more copolymerizable comonomers, of 1) a fluorovinyl ether of formula: CFX═CXOCF₂OR  (I) wherein: a) R is a C₂-C₆ linear or branched perfluoroalkyl group, a C₅-C₆ cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms; b) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be replaced with atoms selected from the group consisting of H, Cl, Br, and I; and c) X is F or H.
 6. The polymer of claim 5 wherein R is CF₂CF₂Y and Y is F or OCF₃.
 7. The polymer of claim 6 wherein each X is F.
 8. The polymer ether of claim 7 wherein Y is F.
 9. The polymer of claim 5 wherein the fluorovinyl ether is copolymerized with at least one comonomer that is a fluorinated compound having at least one polymerizable carbon-carbon double bond.
 10. The polymer of claim 9 wherein the fluorinated compound further comprises at least one atom selected from the group consisting of hydrogen, chlorine, bromine, iodine, and oxygen.
 11. The polymer of claim 5 wherein the the fluorovinyl ether is copolymerized with one or more comonomers that are a C₂-C₈ olefinically unsaturated hydrocarbon.
 12. The polymer of claim 5 wherein the fluorovinyl ether is polymerized with one or more copolymerizable comonomers selected from the following: 1) C₂-C₈ perfluoroolefins; 2) C₂-C₈ fluoroolefins; 3) C₂-C₈ chlorofluoroolefins, C₂-C₈ bromoclhoroolefins, and C₂-C₈ iodofluoroolefins; 4) fluoroalkyl vinyl ethers, having the structure CF₂═CFOR² _(f), wherein R² _(f) is a C₁-C₆ perfluoroalkyl group in which 0 or 1 of the fluorine atoms are replaced with an atom selected from bromine and chlorine; 5) perfluorooxyalkylvinyl ethers of structure CF₂═CFOX^(a) wherein X^(a) is selected from a C₁-C₂ alkyl group, a C₁-C₁₂ oxyalkyl group, and a C₁-C₁₂ fluorooxyalkyl group having at least one ether oxygen,; 6) sulphonic monomers having the structure CF₂═CFOX^(b)SO₂F, wherein X^(b) can be CF₂CF₂, CF₂CF₂CF₂, or CF₂CF(CF₂X^(c)), and wherein X^(c) is selected from F, Cl, Br.
 13. The polymer of claim 12 wherein the perfluoroolefin is selected from tetrafluoroethylene (TFE), hexafluoropropene (HFP), and hexafluoroisobutene.
 14. The polymer of claim 12 wherein the fluoroolefin is selected from the group consisting of vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene, chlorotrifluoroethylene (CTFE), bromotrifluoroethylene, and a fluoroolefin of structure CH₂═CH—R² _(f), wherein R² _(f) is a C₁-C₆ perfluoroalkyl group.
 15. The polymer of claim 12 wherein R² _(f) is selected from a trifluoromethyl group, a bromotrifluoromethyl group, or a heptafluoropropyl group.
 16. The polymer of claim 12 wherein the perfluorooxyalkyl group is the perfluoro-2-propoxypropyl group.
 17. The polymer of claim 5 wherein the amount of fluorovinyl ether polymerized is between about 0.1 mole % and about 20 mole %, the remainder comprising one or more copolymerizable comonomers.
 18. The polymer of claim 17 wherein the amount of fluorvinyl ether polymerized is between about 15 mole % and about 20 mole %, the remainder comprising one or more comonomers.
 19. The polymer of claim 5 wherein the polymer is elastomeric.
 20. The polymer of claim 5 wherein the polymer is plastomeric.
 21. A process for making a fluorovinyl ether of formula CFX═CXOCF₂OR  (I) wherein: 1) R is a C₂-C₆ linear or branched perfluoroalkyl group, a C₅-C₆ cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms; 2) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and 3) X is F or H; comprising the steps of a) contacting hypofluorite, CF₂(OF)₂, with a first olefin of structure R₁R₂C═CR₃R₄, wherein R₁ and R₄ are the same or different and selected from H and F, and R₂ and R₃ are the same or different and selected from H and Cl, to form a first intermediate hypofluorite of structure F—CR₁R₂—CR₃R₄—O—CF₂OF  (VI)  and b) contacting the first intermediate hypofluorite (VI) with a second olefin having structure R₅R₆C¹═C²R₇R₈ to form a second itermediate hypofluorite F—CR₁R₂—CR₃R₄—OCF₂O—C²R₅R₆—C¹R₇R₈—F  (VII) wherein R₅, R₆, R₇, and R₈ are F; or one of R₅, R₆, R₇, and R₈ is a C₁-C₄ linear or branched perfluoroalkyl group and the others of R₅, R₆, R₇, and R₈ are F; or one of R₅, R₆, R₇, and R₈ is a C₁-C₄ linear or branched perfluorooxyalkyl group containing from one to three oxygen atoms and the others of R₅, R₆, R₇, and R₈ are F; or either pairing R₅ and R₇ or R₆ and R₈, together with the carbon atoms to which they are attached, are linked to form a perfluorinated C₅-C₆ cycloalkyl group and the others of R₅, R₆, R₇, and R₈ not so linked are F; and c) when R₂ and R₃ are both Cl, subjecting the second intermediate (VII) to a dehalogenation reaction, or, when one of R₂ and R₃ is H, subjecting the second intermediate (VII) to a dehydrohalogenation reaction;  with the proviso that when one of R₅, R₆, R₇ or R₈ is a C₂-C₄ linear or branched fluoroalky group or a C₂-C₄ linear or branched fluoroalkoxy group comprising from one to three oxygen atoms; then one or two of the remaining three of R₅, R₆, R₇, and R₈ are F and the remaining one or two of R₅, R₆, R₇, R₈ are selected from H, Cl, Br, and I, with the proviso that, where only one of said remaining three of R₅, R₆, R₇, and R₈ is F, then the remaining two of R₅, R₆, R₇, and R₈ are the same and linked to the same carbon atom; and further with the proviso that when R₅ and R₇ together with the carbon to which they are attached, or R₆ and R₈ together with the carbon atom to which they are attached, are linked to form a cyclic then one of the remaining two of R₅, R₆, R₇, and R₈ is F and the other is selected from H, Cl, Br, and I.
 22. The process of claim 21 wherein the second olefin is reacted with hypofluorite in place of first olefin and the first intermediate hypofluorite is then reacted with the first olefin.
 23. The process of claim 21 wherein the contacting is in a continuous process in which the mole amount of hypofluorite contacted is equal to or greater than the mole amount of first olefin R₁R₂C═R₃R₄ contacted and further wherein the residence time in the reactor is between about 0.05 and about 120 seconds, the temperature is between about −40° and about −150° C., and the first intermediate hypofluorite of the reaction of the first olefin with hypofluotite is continuously reacted with the second olefin.
 24. A process according to claim 21 wherein the concentration of second olefin R₅R₆C═CR₇R₈ is constant and greater than about 0.01M and the temperature is between about −20° C. to −100° C.
 25. The process of claim 24 wherein the concentration of second olefin is equal to or greater than about 3M.
 26. In a process for making a fluorovinyl ether of structure: CFX═CXOCF₂OR  (I) wherein: 1) R is a C₂-C₆ linear or branched perfluoroalkyl group, a C₅-C₆ cyclic perfluoroalkyl group, or a linear or branched perfluorooxyalkyl group comprising 2 to 6 carbon atoms and 1 to 3 oxygen atoms; 2) up to two fluorine atoms of the perfluoroalkyl group or the perfluorooxyalkyl group can be independently replaced with an atom selected from the group consisting of H, Cl, Br, and I; and 3) X is F or H; the step of: contacting a first fluoroalkene with a hypofluorite to form a first intermediate; then contacting the first intermediate with a second fluoroalkene to form a second intermediate; 1) the hypofluorite is of structure X₁X₂C(OF)₂ wherein X₁ and X₂ are the same or different and selected from F and CF₃; and 2) the first and second fluoroalkenes may be the same or different and are selected from R^(A) ₁R^(A) ₂C═CR^(A) ₃R^(A) ₄ and R^(A) ₄R^(A) ₅C═CR^(A) ₇R^(A) ₈ wherein each of R^(A) ₁, R^(A) ₂, R^(A) ₃, R^(A) ₄, R^(A) ₅, R^(A) ₆, R^(A) ₇, and R^(A) ₈ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, —CF₂OSO₂F, —SO₂F, —C(O)F, C₁-C₅ linear or branched perfluoroalkyl, and linear or branched oxyperfluoroalkyl. 